1. Exciton coupling model for the emergence of second harmonic generation from assemblies of centrosymmetric molecules.
- Author
-
Snyder GR, Chowdhury AU, and Simpson GJ
- Subjects
- Computer Simulation, Dimerization, Quantum Theory, Thermodynamics, Anthraquinones chemistry, Butadienes chemistry, Models, Chemical
- Abstract
A simple model is presented for interpreting the presence of substantial second harmonic generation (SHG) activity from assemblies of centrosymmetric molecular building blocks. Using butadiene as a computationally tractable centrosymmetric model system, time-dependent Hartree-Fock calculations of the nonlinear polarizability of butadiene dimer were well-described through exciton coupling arguments based on the electronic structure of the monomer and the relative orientation between the monomers within the dimer. Experimental studies of the centrosymmetric molecule 2,6-di-tert-butylanthraquinone suggest the formation of a combination of SHG-active and SHG-inactive crystal forms. The structure for the centrosymmetric form is known, serving as a negative control for the model, while the presence of an additional SHG-active metastable form is consistent with predictions of the model for alternative molecular packing configurations.
- Published
- 2014
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